ACS Organic & Inorganic AuPub Date : 2024-06-05DOI: 10.1021/acsorginorgau.4c0003210.1021/acsorginorgau.4c00032
Badaraita Gorachand, Gundam Surendra Reddy and Dhevalapally B. Ramachary*,
{"title":"Direct Organocatalytic Chemoselective Synthesis of Pharmaceutically Active 1,2,3-Triazoles and 4,5′-Bitriazoles","authors":"Badaraita Gorachand, Gundam Surendra Reddy and Dhevalapally B. Ramachary*, ","doi":"10.1021/acsorginorgau.4c0003210.1021/acsorginorgau.4c00032","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00032https://doi.org/10.1021/acsorginorgau.4c00032","url":null,"abstract":"<p >Carbonyl-containing 1,4,5-trisubstituted- and 1,4-disubstituted-1,2,3-triazoles are well-known for their wide range of applications in pharmaceutical and medicinal chemistry, but their high-yielding metal-free synthesis has always remained challenging, as no comprehensive protocol has been outlined to date. Owing to their structural and medicinal importance, herein, we synthesized various carbonyl-containing 1,4,5-trisubstituted- and 1,4-disubstituted-1,2,3-triazoles and unsymmetrical 4,5′-bitriazoles with high yields and chemo-/regioselectivity from the library of 2,4-diketoesters and azides in a sequential one-pot manner through the combination of organocatalytic enolization, in situ [3 + 2]-cycloaddition, and hydrolysis reactions. The commercial availability of the starting materials/catalysts, diverse substrate scope, performance in a one-pot manner, chemo-/regioselectivity of organo-click reaction, quick synthesis of unsymmetrical 4,5′-bitriazoles, a large number of synthetic applications, and numerous medicinal applications of carbonyl-containing 1,2,3-triazoles are the key attractions of this metal-free organo-click work.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00032","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142402780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Organic & Inorganic AuPub Date : 2024-06-04DOI: 10.1021/acsorginorgau.4c0003010.1021/acsorginorgau.4c00030
Jordi C. J. Hintzen, Shitanshu Devrani, Andrew J. Carrod, M. Bahadir Bayik, Daniel Tietze and Alesia A. Tietze*,
{"title":"Fluorescence Labeling of Peptides: Finding the Optimal Protocol for Coupling Various Dyes to ATCUN-like Structures","authors":"Jordi C. J. Hintzen, Shitanshu Devrani, Andrew J. Carrod, M. Bahadir Bayik, Daniel Tietze and Alesia A. Tietze*, ","doi":"10.1021/acsorginorgau.4c0003010.1021/acsorginorgau.4c00030","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00030https://doi.org/10.1021/acsorginorgau.4c00030","url":null,"abstract":"<p >Labeling of peptides and proteins with fluorescent dyes is a key step in functionalizing these structures for a wide array of biological assays. However, coupling strategies of such dyes have not been optimized for the most common compounds, while this step is typically the most precious and costly of the whole synthesis. We searched for the best conditions for attachment of the most widely used fluorescent dyes such as 6-carboxyfluorescein, Rhodamine B, and BODIPY-FL to peptides, where amino terminal Cu(II) and Ni(II) binding site (ATCUN) peptides were used as a model system. Surprisingly, conventional methods of dye attachment proved to not be satisfactory and yielded poor efficiency results. We have discovered that when labeling primary amines on peptides, the uncommon synthesis of activated pentafluorophenol (PFP) esters is the most efficient strategy, expedited by microwave irradiation. Coupling to secondary amines is achieved most efficiently through conventional coupling reagents such as HATU and PyBOP. Furthermore, we have employed our fluorescently labeled ATCUN peptides in studies for Cu(II) and Ni(II) sensing, showing that changing the fluorophore does not significantly affect the fluorescence quenching process and discovering the optimal linker length between the ATCUN core and the dye, expanding the repertoire of fluorophores that can be used in this application.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00030","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142402779","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Organic & Inorganic AuPub Date : 2024-05-16DOI: 10.1021/acsorginorgau.4c0001310.1021/acsorginorgau.4c00013
Ryuki Sumida, Lorenzo Catti and Michito Yoshizawa*,
{"title":"Bioinspired Binding and Conversion of Linear Monoterpenes by Polyaromatic Coordination Capsules","authors":"Ryuki Sumida, Lorenzo Catti and Michito Yoshizawa*, ","doi":"10.1021/acsorginorgau.4c0001310.1021/acsorginorgau.4c00013","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00013https://doi.org/10.1021/acsorginorgau.4c00013","url":null,"abstract":"<p >Linear monoterpenes, versatile reaction biosubstrates, are bound and subsequently converted to various cyclic monomers and oligomers with excellent selectivity and efficiency, <i>only</i> in natural enzymes. We herein report bioinspired functions of synthetic polyaromatic cavities toward linear monoterpenes in the solution and solid states. The cavities are provided by polyaromatic coordination capsules, formed by the assembly of Pt(II) ions and bent bispyridine ligands with two anthracene panels. By using the capsule cavities, the selective binding of citronellal from mixtures with other monoterpenes and its preferential vapor binding over its derivatives are demonstrated in water and in the solid state, respectively. The capsule furthermore extracts <i>p</i>-menthane-3,8-diol, with high product- and stereoselectivity, from a reaction mixture obtained by the acid-catalyzed cyclization of citronellal in water. Thanks to the inner and outer polyaromatic cavities, the catalytic cyclization-dimerization of vaporized citronellal efficiently proceeds in the acid-loaded capsule solid and product/stereoselectively affords <i>p</i>-menthane-3,8-diol citronellal acetal (∼330% yield based on the capsule) under ambient conditions. The solid capsule reactor can be reused at least 5 times with enhanced conversion. The present study opens up a new approach toward mimicking terpene biosynthesis via synthetic polyaromatic cavities.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00013","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141959334","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Organic & Inorganic AuPub Date : 2024-05-15DOI: 10.1021/acsorginorgau.4c0002810.1021/acsorginorgau.4c00028
Serhii Holovach, Illia Poroshyn, Kostiantyn P. Melnykov, Oleksandr S. Liashuk, Olena O. Pariiska, Sergey V. Kolotilov, Alexander B. Rozhenko, Dmytro M. Volochnyuk and Oleksandr O. Grygorenko*,
{"title":"Parallel Minisci Reaction of gem-Difluorocycloalkyl Building Blocks","authors":"Serhii Holovach, Illia Poroshyn, Kostiantyn P. Melnykov, Oleksandr S. Liashuk, Olena O. Pariiska, Sergey V. Kolotilov, Alexander B. Rozhenko, Dmytro M. Volochnyuk and Oleksandr O. Grygorenko*, ","doi":"10.1021/acsorginorgau.4c0002810.1021/acsorginorgau.4c00028","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00028https://doi.org/10.1021/acsorginorgau.4c00028","url":null,"abstract":"<p >Parallel Minisci reactions of nonfluorinated and <i>gem</i>-difluorinated C<sub>4</sub>–C<sub>7</sub> cycloalkyl building blocks (trifluoroborates and carboxylic acids) with a series of electron-deficient heterocycles were studied. A comparison of the reaction’s outcome revealed better product yields in the case of carboxylic acids as the radical precursors in most cases, albeit these reagents were used with three-fold excess under optimized conditions. The nature of the heterocyclic core was found to be important for successful incorporation of the cycloalkyl fragment. The impact of the CF<sub>2</sub> moiety on the oxidation potential of fluorinated cycloalkyl trifluoroborates and the reaction outcome, in general, was also evaluated.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00028","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141959333","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Organic & Inorganic AuPub Date : 2024-05-07DOI: 10.1021/acsorginorgau.4c0000910.1021/acsorginorgau.4c00009
Steffan K. Kristensen, Alexander Ahrens, Bjarke S. Donslund and Troels Skrydstrup,
{"title":"Perspective on the Development of Monomer Recovery Technologies from Plastics Designed to Last","authors":"Steffan K. Kristensen, Alexander Ahrens, Bjarke S. Donslund and Troels Skrydstrup, ","doi":"10.1021/acsorginorgau.4c0000910.1021/acsorginorgau.4c00009","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00009https://doi.org/10.1021/acsorginorgau.4c00009","url":null,"abstract":"<p >In order to prevent the current unsustainable waste handling of the enormous volumes of end-of-use organic polymer material sent to landfilling or incineration, extensive research efforts have been devoted toward the development of appropriate solutions for the recycling of commercial thermoset polymers. The inability of such cross-linked polymers to be remelted once cured implies that mechanical recycling processes used for thermoplastic materials do not translate to the recycling of thermoset polymers. Moreover, the structural diversity within the materials from the use of different monomers as well as the use of such polymers for the fabrication of fiber-reinforced polymer composites make recycling of these materials highly challenging. In this Perspective, depolymerization strategies for thermoset polymers are discussed with an emphasis on recent advancements within our group on recovering polymer building blocks from polyurethane (PU) and epoxy-based materials. While these two represent the largest thermoset polymer groups with respect to the production volumes, the recycling landscapes for these classes of materials are vastly different. For PU, increased collaboration between academia and industry has resulted in major advancements within solvolysis, acidolysis, aminolysis, and split-phase glycolysis for polyol recovery, where several processes are being evaluated for further scaling studies. For epoxy-based materials, the molecular skeleton has no obvious target for chemical scission. Nevertheless, we have recently demonstrated the possibility of the disassembly of the epoxy polymer in fiber-reinforced composites for bisphenol A (BPA) recovery through catalytic C–O bond cleavage. Furthermore, a base promoted cleavage developed by us and others shows tremendous potential for the recovery of BPA from epoxy polymers. Further efforts are still required for evaluating the suitability of such monomer recovery strategies for epoxy materials at an industrial scale. Nonetheless, recent advancements as illustrated with the presented chemistry suggest that the future of thermoset polymer recycling could include processes that emphasize monomer recovery in an energy efficient manner for closed-loop recycling.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00009","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141957246","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Steffan K. Kristensen, Alexander Ahrens, Bjarke S. Donslund, Troels Skrydstrup
{"title":"Perspective on the Development of Monomer Recovery Technologies from Plastics Designed to Last","authors":"Steffan K. Kristensen, Alexander Ahrens, Bjarke S. Donslund, Troels Skrydstrup","doi":"10.1021/acsorginorgau.4c00009","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00009","url":null,"abstract":"In order to prevent the current unsustainable waste handling of the enormous volumes of end-of-use organic polymer material sent to landfilling or incineration, extensive research efforts have been devoted toward the development of appropriate solutions for the recycling of commercial thermoset polymers. The inability of such cross-linked polymers to be remelted once cured implies that mechanical recycling processes used for thermoplastic materials do not translate to the recycling of thermoset polymers. Moreover, the structural diversity within the materials from the use of different monomers as well as the use of such polymers for the fabrication of fiber-reinforced polymer composites make recycling of these materials highly challenging. In this Perspective, depolymerization strategies for thermoset polymers are discussed with an emphasis on recent advancements within our group on recovering polymer building blocks from polyurethane (PU) and epoxy-based materials. While these two represent the largest thermoset polymer groups with respect to the production volumes, the recycling landscapes for these classes of materials are vastly different. For PU, increased collaboration between academia and industry has resulted in major advancements within solvolysis, acidolysis, aminolysis, and split-phase glycolysis for polyol recovery, where several processes are being evaluated for further scaling studies. For epoxy-based materials, the molecular skeleton has no obvious target for chemical scission. Nevertheless, we have recently demonstrated the possibility of the disassembly of the epoxy polymer in fiber-reinforced composites for bisphenol A (BPA) recovery through catalytic C–O bond cleavage. Furthermore, a base promoted cleavage developed by us and others shows tremendous potential for the recovery of BPA from epoxy polymers. Further efforts are still required for evaluating the suitability of such monomer recovery strategies for epoxy materials at an industrial scale. Nonetheless, recent advancements as illustrated with the presented chemistry suggest that the future of thermoset polymer recycling could include processes that emphasize monomer recovery in an energy efficient manner for closed-loop recycling.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140887135","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Organic & Inorganic AuPub Date : 2024-04-19DOI: 10.1021/acsorginorgau.3c0007010.1021/acsorginorgau.3c00070
Larissa A. Casper, Katharina L. Deuter, Anja Rehse and Rainer F. Winter*,
{"title":"Dimerization of 9-Phenyl-ferroceno[2,3]indenylmethyl Radicals: Electrochemical and Spectroelectrochemical Studies","authors":"Larissa A. Casper, Katharina L. Deuter, Anja Rehse and Rainer F. Winter*, ","doi":"10.1021/acsorginorgau.3c0007010.1021/acsorginorgau.3c00070","DOIUrl":"https://doi.org/10.1021/acsorginorgau.3c00070https://doi.org/10.1021/acsorginorgau.3c00070","url":null,"abstract":"<p >We report on three new 9-phenyl-substituted ferroceno[2,3]indenylmethylium dyes <b>1</b><sup><b>+</b></sup>–<b>3</b><sup><b>+</b></sup> with electron-donating (OMe, Me) or electron-withdrawing (CF<sub>3</sub>) substituents. Complexes <b>1</b><sup><b>+</b></sup>–<b>3</b><sup><b>+</b></sup> exist as racemic mixtures of <i>Rp</i> and <i>Sp</i> enantiomers. Pyramidalization at the methyl C atom in the precursor carbinol species <b>1-OH</b>–<b>3-OH</b> or the corresponding one-electron reduced radicals induces a second stereocenter, as the 9-phenyl substituent may reside in an <i>endo</i> or an <i>exo</i> position. Indeed, alcohol <b>2-OH</b> crystallizes as a racemate of <i>Rp</i>,<i>S</i> and <i>Sp</i>,<i>R</i> isomers. Cationic complexes <b>1</b><sup><b>+</b></sup>–<b>3</b><sup><b>+</b></sup> are of deep green color and show intense electronic absorption in the visible. The oxidation and reduction processes are thoroughly investigated by means of cyclic voltammetry and UV/vis/NIR spectroelectrochemistry, the latter showing their electrochromic behavior. <i>T</i>-dependent EPR spectroscopy, EPR spin counting at 20 °C, as well as the UV/vis/NIR spectra of the reduced samples suggest that the one-electron reduced, neutral radicals dimerize nearly quantitatively (≥99.98%). Chemical reduction of <b>2</b><sup><b>+</b></sup> furnished an isomeric mixture of dimeric <b>2</b>–<b>2</b>. As was shown by cyclic voltammetry and UV/vis/NIR spectroelectrochemistry, the latter dimer redissociates to monomers <b>2</b><sup><b>+</b></sup> upon oxidation, thereby closing a reversible cycle of redox-induced C–C bond making and breaking.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.3c00070","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141954741","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Organic & Inorganic AuPub Date : 2024-03-26DOI: 10.1021/acsorginorgau.4c0000510.1021/acsorginorgau.4c00005
Peter J. Canfield*, Jeffrey R. Reimers* and Maxwell J. Crossley*,
{"title":"“Polytopal Rearrangement Model of Stereoisomerization” and Its Potential as the Basis for a Systematic Model of All Stereoisomerism","authors":"Peter J. Canfield*, Jeffrey R. Reimers* and Maxwell J. Crossley*, ","doi":"10.1021/acsorginorgau.4c0000510.1021/acsorginorgau.4c00005","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00005https://doi.org/10.1021/acsorginorgau.4c00005","url":null,"abstract":"<p >The term “polytopal rearrangement” describes any shape changing process operating on a coordination “polyhedron”─the solid figure defined by the positions of the ligand atoms directly attached to the central atom of a coordination entity. Developed in the latter third of the last century, the polytopal rearrangement model of stereoisomerization is a general mathematical approach for analyzing and accommodating the complexity of such processes for any coordination number. The motivation for the model was principally to deal with the complexity, such as Berry pseudorotation in pentavalent phosphorus species, arising from rearrangements in inorganic coordination complexes of higher coordination numbers. The model is also applicable to lower coordination centers, for example, thermal “inversion” at nitrogen in NH<sub>3</sub> and amines. We present the history of the model focusing on its essential features, and review some of the more subtle aspects addressed in recent literature. We then introduce a more detailed and rigorous modern approach for describing such processes using an assembly of existing concepts, with the addition of formally described terminology and representations. In our outlook, we contend that the rigorous and exhaustive application of the principles of the polytopal rearrangement model, when combined with torsional isomerism, will provide a basis for a mathematically complete, general, and systematic classification for all stereoisomerism and stereoisomerization. This is essential for comprehensively mapping chemical structure and reaction spaces.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00005","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141959248","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Peter J. Canfield, Jeffrey R. Reimers, Maxwell J. Crossley
{"title":"“Polytopal Rearrangement Model of Stereoisomerization” and Its Potential as the Basis for a Systematic Model of All Stereoisomerism","authors":"Peter J. Canfield, Jeffrey R. Reimers, Maxwell J. Crossley","doi":"10.1021/acsorginorgau.4c00005","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00005","url":null,"abstract":"The term “polytopal rearrangement” describes any shape changing process operating on a coordination “polyhedron”─the solid figure defined by the positions of the ligand atoms directly attached to the central atom of a coordination entity. Developed in the latter third of the last century, the polytopal rearrangement model of stereoisomerization is a general mathematical approach for analyzing and accommodating the complexity of such processes for any coordination number. The motivation for the model was principally to deal with the complexity, such as Berry pseudorotation in pentavalent phosphorus species, arising from rearrangements in inorganic coordination complexes of higher coordination numbers. The model is also applicable to lower coordination centers, for example, thermal “inversion” at nitrogen in NH<sub>3</sub> and amines. We present the history of the model focusing on its essential features, and review some of the more subtle aspects addressed in recent literature. We then introduce a more detailed and rigorous modern approach for describing such processes using an assembly of existing concepts, with the addition of formally described terminology and representations. In our outlook, we contend that the rigorous and exhaustive application of the principles of the polytopal rearrangement model, when combined with torsional isomerism, will provide a basis for a mathematically complete, general, and systematic classification for all stereoisomerism and stereoisomerization. This is essential for comprehensively mapping chemical structure and reaction spaces.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140311639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Clarabella J. Li, Joseph W. Ziller, Jeffrey M. Barlow, Jenny Y. Yang
{"title":"Aqueous Electrochemical and pH Studies of Redox-Active Guanidino Functionalized Aromatics for CO2 Capture","authors":"Clarabella J. Li, Joseph W. Ziller, Jeffrey M. Barlow, Jenny Y. Yang","doi":"10.1021/acsorginorgau.3c00066","DOIUrl":"https://doi.org/10.1021/acsorginorgau.3c00066","url":null,"abstract":"Escalating levels of carbon dioxide (CO<sub>2</sub>) in the atmosphere have motivated interest in CO<sub>2</sub> capture and concentration from dilute streams. A guanidino-functionalized aromatic 1,4-bis(tetramethylguanidino)benzene (1,4-btmgb) was evaluated both as a redox-active sorbent and as a pH swing mediator for electrochemical CO<sub>2</sub> capture and concentration. Spectroscopic and crystallographic studies demonstrate that 1,4-btmgb reacts with CO<sub>2</sub> in water to form 1,4-btmgbH<sub>2</sub>(HCO<sub>3</sub><sup>–</sup>)<sub>2</sub>. The product suggests that 1,4-btmgb could be used in an aqueous redox pH swing cycle for the capture and concentration of CO<sub>2</sub>. The synthesis and characterization of the mono- and diprotonated forms (1,4-btmgbH<sup>+</sup> and 1,4-btmgbH<sub>2</sub><sup>2+</sup>) and their p<i>K</i><sub>a</sub> values were measured to be 13.5 and 11.0 in water, respectively. Electrochemical pH swing experiments indicate the formation of an intermediate radical species and other degradation pathways, which ultimately inhibited fully reversible redox-induced pH cycling.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140202656","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}